CN113117455A - Application of choline chloride-glycerol eutectic solvent in absorbing HCl gas - Google Patents
Application of choline chloride-glycerol eutectic solvent in absorbing HCl gas Download PDFInfo
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- CN113117455A CN113117455A CN202110386018.XA CN202110386018A CN113117455A CN 113117455 A CN113117455 A CN 113117455A CN 202110386018 A CN202110386018 A CN 202110386018A CN 113117455 A CN113117455 A CN 113117455A
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- choline chloride
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- 239000002904 solvent Substances 0.000 title claims abstract description 56
- 230000005496 eutectics Effects 0.000 title claims abstract description 47
- 229960001231 choline Drugs 0.000 title claims abstract description 42
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 title claims abstract description 42
- NQCBIMOYRRMVNA-UHFFFAOYSA-N propane-1,2,3-triol;hydrochloride Chemical compound Cl.OCC(O)CO NQCBIMOYRRMVNA-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000010521 absorption reaction Methods 0.000 claims abstract description 94
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 53
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical group [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims abstract description 17
- 235000019743 Choline chloride Nutrition 0.000 claims abstract description 17
- 229960003178 choline chloride Drugs 0.000 claims abstract description 17
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 101150071434 BAR1 gene Proteins 0.000 claims description 2
- 230000005587 bubbling Effects 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 abstract description 3
- 230000002745 absorbent Effects 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 59
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 16
- 235000011187 glycerol Nutrition 0.000 description 14
- 238000005303 weighing Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/202—Alcohols or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/204—Amines
- B01D2252/20478—Alkanolamines
- B01D2252/20484—Alkanolamines with one hydroxyl group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/50—Combinations of absorbents
- B01D2252/504—Mixtures of two or more absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2045—Hydrochloric acid
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention provides an application of a choline chloride-glycerol eutectic solvent in absorbing HCl gas. The eutectic solvent consists of a component A and a component B according to a certain molar ratio, wherein the component A is glycerol, and the component B is choline chloride. Through a large number of experimental screens, the eutectic solvent (ChCl-Gly) formed by choline chloride (ChCl) and glycerol (Gly) has the best performance by taking the ChCl-Gly (1:1.5) as an absorbent; the eutectic solvent can be used for absorbing HCl at room temperature and higher temperature, and the absorption performance of the eutectic solvent is kept basically unchanged after 20 times of cyclic absorption.
Description
Technical Field
The invention belongs to the field of chemical absorption and separation, and particularly relates to application of a choline chloride-glycerol eutectic solvent in absorbing HCl gas.
Background
The tail gas HCl generated in the reaction processes of chlorination, dechlorination and the like in the chlor-alkali industry has irritation and corrosivity and is harmful to the environment and human health. Meanwhile, HCl is a basic raw material for producing important fine chemicals in the chemical industry, such as chloropropene monomer synthesis, methyl chloride and other alkyl chlorides.
The HCl-containing gas tail gas is treated by a batch absorption method to obtain low-value dilute hydrochloric acid by-product, or directly neutralized by limestone or waste lye before discharge. And for a large amount of tail gas, concentrated hydrochloric acid is prepared by using a multi-stage or continuous absorption device and then is sold.
Although the aqueous solution absorption HCl process is widely applied to the industry, the process has a long-standing problem due to the low added value of the dilute hydrochloric acid and the serious equipment corrosion problem. In contrast, the value and market demand for dry HCl gas is increasing. Therefore, it is necessary to develop a novel non-aqueous solvent to absorb and separate the dry HCl gas from the HCl gas-containing tail gas, so as to realize high value-added utilization of the HCl gas resource.
For this purpose, attempts have been made to separate HCl by absorption using organic solvents. Such as document 1 (solubility of trifluoromethane and hydrogen chloride gas in different solvents [ J)]College chemical engineering reports 2008(1) (1-5) report that HCl is separated by absorption using various traditional organic solvents, and researches show that alcohol solvents such as methanol, butanol and glycerol have a good absorption effect on HCl, but since low-boiling-point solvents such as methanol and butanol can volatilize, HCl gas obtained after absorption liquid desorption is often mixed with steam of the solvents, and the purity of the HCl gas is difficult to reach 99.5%. Document 2 (investigation of separation of hydrogen chloride and sulfur dioxide by non-aqueous solvent [ J)]Najing university journal (Nature science), 2016, 52(2): 221-2An absorption of 0.230 g (HCl)/g (glycerol) was obtained at 40 ℃ and 1 bar. But the viscosity of the glycerol at the temperature of 40 ℃ is very high, the HCl absorption rate is very slow, and the absorption mass transfer resistance is very high, so that the glycerol is not beneficial to industrial operation and use.
The patent document of application No. 201811583885.7 provides a method for absorbing and separating HCl from an HCl mixed gas by using an alcohol organic solvent diethylene glycol as an absorbent, and although the absorption effect of 0.20 to 0.40 g (HCl)/g (diethylene glycol) is obtained, HCl with a mass fraction of 5 wt% cannot be completely desorbed, so that the recycle performance of diethylene glycol is greatly reduced, and the method is not beneficial to industrial operation.
Disclosure of Invention
The invention aims to provide application of a choline chloride-glycerol eutectic solvent aiming at the problem of absorbing HCl gas from tail gas containing HCl gas.
The inventor of the application finds that the HCl gas can be reversibly and efficiently absorbed by a eutectic solvent formed by choline chloride and glycerol. Choline chloride (ChCl) and glycerol (Gly) are mixed according to different molar ratios, and the mixture is heated and stirred at the temperature of 80-90 ℃ until a liquid phase system is uniform, so that choline chloride-glycerol eutectic solvents (ChCl-Gly) with different proportions are obtained; HCl gas is introduced into the ChCl-Gly, and then the HCl gas can be absorbed. After absorption, heating at 90-100 ℃, and desorbing to release HCl gas with the purity of 99.5%.
The invention provides an application of a choline chloride-glycerol eutectic solvent in absorbing HCl gas.
The invention also provides a method for absorbing HCl gas by using the choline chloride-glycerol eutectic solvent, which comprises the following steps: and (2) introducing gas containing HCl into an absorption bottle filled with the choline chloride-glycerol eutectic solvent, absorbing the HCl gas into a liquid phase in a bubbling mode, and discharging the residual gas phase from an exhaust port of the absorption bottle to obtain the choline chloride-glycerol eutectic solvent and the residual gas phase for absorbing the HCl gas respectively.
Preferably, the molar ratio of choline chloride to glycerol in the choline chloride-glycerol eutectic solvent is 1: 1.5-1: 2.5; more preferably, the molar ratio is 1: 1.5.
Preferably, the temperature for absorbing HCl by the choline chloride-glycerol eutectic solvent is 25-60 ℃, and the absorption time is 20-8 min; more preferably, the absorption temperature is 25 ℃ and the absorption time is 20 min.
Preferably, the absorption partial pressure of the HCl gas is 0.15 bar-1 bar; more preferably, the partial pressure of absorption is 0.15 bar.
Preferably, the method further comprises the step of heating the choline chloride-glycerol eutectic solvent for absorbing the HCl gas, so that the choline chloride-glycerol eutectic solvent for absorbing the HCl gas is desorbed to release HCl gas with the purity of 99.5%, and thus the cyclic utilization of the choline chloride-glycerol eutectic solvent is realized.
Preferably, the heating temperature is 90-100 ℃, and the heating time is 30 min.
The invention has the following beneficial effects:
(1) the choline chloride-glycerol eutectic solvent is used for absorbing HCl gas for the first time, so that the HCl can be reversibly and efficiently absorbed, and the aim of separating and recycling a pure HCl gas resource from the HCl-containing gas is fulfilled.
(2) Through a large number of experimental screens, the choline chloride-glycerol eutectic solvent with the molar ratio of 1:1.5 has comprehensive indexes such as absorption capacity, absorption rate, reversible absorption performance, HCl purity obtained by desorption and the like, and is comprehensively superior to liquid solvent absorbents reported in the prior literatures and patents.
(3) After the choline chloride-glycerol eutectic solvent absorbs HCl gas, complete desorption can be achieved only by a heating mode, so that cyclic application is achieved, the absorption performance is kept unchanged after 20-time cyclic testing, and compared with a traditional aqueous solution evaporation method, equipment corrosion and desorption energy consumption are greatly reduced.
Drawings
Figure 1 shows the HCl absorption cycle performance of example 1.
FIG. 2 shows the HCl absorption rate curves for examples 1 and 4-6.
FIG. 3 shows the HCl absorption amounts of examples 1 and 4 to 10.
Fig. 4 shows a comparison of HCl absorption rates for example 1 and comparative example 3.
FIG. 5 shows HCl absorption device diagrams of examples and comparative examples, in FIG. 5, V1: gas mixing bottle, V2: gas absorption bottle, F1~F2: a rotameter; j. the design is a square1~J4: and a stop valve.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: choline chloride-glycerol eutectic solvent with molar ratio of 1:1.5
(1) Mixing the dried and dehydrated choline chloride (ChCl) and glycerol (Gly) according to the molar ratio of ChCl to Gly =1:1.5, and stirring at 80-90 ℃ until a liquid phase system is uniform to obtain a choline chloride-glycerol eutectic solvent (ChCl-Gly (1: 1.5));
(2) accurately weighing the mass of an absorption bottle with the volume of 10mL, filling a choline chloride-glycerol eutectic solvent ChCl-Gly (1:1.5) and weighing the total mass (the mass of a sample is about 2g, and the accuracy is 0.0001 g), then introducing HCl pure gas into the absorption bottle for absorption, weighing the mass of the absorption bottle every 2min, recording, and stopping weighing until the difference between the front and the back of weighing is 0.005 g; repeating the absorption experiment step for 3 times to eliminate experiment errors, wherein the error value is +/-2%; the calculated HCl absorption capacity is 0.303g (HCl)/g (ChCl-Gly) at 25 deg.C and HCl partial pressure of 1bar, and the absorption equilibrium time is 20 min;
(3) moving a ChCl-Gly (1:1.5) sample after absorbing HCl and an absorption bottle to a heating desorption device together, heating and desorbing at the temperature of 90-100 ℃ for 30min to obtain HCl gas with the purity of 99.5%, wherein the HCl content in the desorbed ChCl-Gly (1:1.5) sample is less than or equal to 0.001 g (HCl)/g (ChCl-Gly);
(4) and (3) repeating the operations according to the steps (2) and (3) on the sample of the ChCl-Gly (1:1.5) desorbed in the step (3), wherein the absorption capacity can still reach the level of about 0.300 g (HCl)/g (ChCl-Gly) after 20 times of cycle tests.
Example 2: choline chloride-glycerol eutectic solvent with molar ratio of 1:2.0
Example 2 was substantially the same as example 1 except that the molar ratio of choline chloride (ChCl) to glycerol (Gly) was modified to ChCl: Gly =1: 2.0. When the temperature is 25 ℃ and the HCl partial pressure is 1bar, the absorption capacity of HCl is 0.291 g (HCl)/g (ChCl-Gly), the absorption equilibrium time is 20min, and the HCl gas with the purity of 99.5% can be obtained by heating and desorbing at 90-100 ℃, and after 20 times of cycle tests, the absorption capacity can still reach the level of about 0.290 g (HCl)/g (ChCl-Gly).
Example 3: choline chloride-glycerol eutectic solvent with molar ratio of 1:2.5
Example 3 was substantially the same as example 1 except that the molar ratio of choline chloride (ChCl) to glycerol (Gly) was modified to ChCl: Gly =1: 2.5. When the temperature is 25 ℃ and the HCl partial pressure is 1bar, the absorption capacity of HCl is 0.279g (HCl)/g (ChCl-Gly), the absorption equilibrium time is 20min, the HCl gas with the purity of 99.5 percent can be obtained by heating and desorbing at 90-100 ℃, and the absorption capacity can still reach the level of about 0.276 g (HCl)/g (ChCl-Gly) after 20 times of cycle tests.
Example 4: choline chloride-glycerol eutectic solvent with molar ratio of 1:1.5
Example 4 the temperature of only step (2) was modified to 40 ℃ substantially the same as in example 1. When the temperature is 40 ℃ and the HCl partial pressure is 1bar, the absorption capacity of HCl is 0.242 g (HCl)/g (ChCl-Gly), the absorption equilibrium time is 16 min, 99.5% purity HCl gas can be obtained by heating and desorption at 90-100 ℃, and the absorption capacity can still reach the level of about 0.242 g (HCl)/g (ChCl-Gly) after 20 times of cycle tests.
Example 5: choline chloride-glycerol eutectic solvent with molar ratio of 1:1.5
Example 5 was substantially the same as example 1 except that the temperature of step (2) was modified to 50 ℃. When the temperature is 50 ℃ and the HCl partial pressure is 1bar, the absorption capacity of HCl is 0.208 g (HCl)/g (ChCl-Gly), the absorption equilibrium time is 8min, the HCl gas with the purity of 99.5% can be obtained by heating and desorbing at 90-100 ℃, and the absorption capacity can still reach the level of about 0.207 g (HCl)/g (ChCl-Gly) after 20 times of cycle tests.
Example 6: choline chloride-glycerol eutectic solvent with molar ratio of 1:1.5
Example 6 was substantially the same as example 1 except that the temperature of step (2) was modified to 60 ℃. When the temperature is 60 ℃ and the HCl partial pressure is 1bar, the absorption capacity of HCl is 0.175 g (HCl)/g (ChCl-Gly), the absorption equilibrium time is 8min, the HCl gas with the purity of 99.5% can be obtained by heating and desorbing at 90-100 ℃, and the absorption capacity can still reach the level of about 0.175 g (HCl)/g (ChCl-Gly) after 20 times of cycle tests.
Example 7: choline chloride-glycerol eutectic solvent with molar ratio of 1:1.5
Example 7 substantially the same as example 1, except that the HCl pure gas of the step (2) was modified to a mixed gas containing HCl (composed of 15% v/v HCl and 85% v/v propylene). When the temperature is 25 ℃ and the HCl partial pressure is 0.15bar, the absorption capacity of HCl is 0.175 g (HCl)/g (ChCl-Gly), the absorption equilibrium time is 20min, 99.5 percent of HCl gas can be obtained by heating and desorbing at 90-100 ℃, and after 20 times of cycle tests, the absorption capacity can still reach the level of about 0.175 g (HCl)/g (ChCl-Gly).
Example 8: choline chloride-glycerol eutectic solvent with molar ratio of 1:1.5
Example 8 was substantially the same as example 7 except that the temperature of step (2) was modified to 40 ℃. When the temperature is 40 ℃ and the HCl partial pressure is 0.15bar, the absorption capacity of HCl is 0.133g (HCl)/g (ChCl-Gly), the absorption equilibrium time is 16 min, 99.5 percent of HCl gas can be obtained by heating and desorbing at 90-100 ℃, and after 20 times of cycle tests, the absorption capacity can still reach the level of about 0.133g (HCl)/g (ChCl-Gly).
Example 9: choline chloride-glycerol eutectic solvent with molar ratio of 1:1.5
Example 9 was substantially the same as example 7 except that the temperature of step (2) was modified to 50 ℃. When the temperature is 50 ℃ and the HCl partial pressure is 0.15bar, the absorption capacity of HCl is 0.102 g (HCl)/g (ChCl-Gly), the absorption equilibrium time is 8min, 99.5 percent of HCl gas can be obtained by heating and desorbing at 90-100 ℃, and after 20 times of cycle tests, the absorption capacity can still reach the level of about 0.101 g (HCl)/g (ChCl-Gly).
Example 10: choline chloride-glycerol eutectic solvent with molar ratio of 1:1.5
Example 10 was substantially the same as example 7 except that the temperature of step (2) was modified to 60 ℃. When the temperature is 60 ℃ and the HCl partial pressure is 0.15bar, the absorption capacity of HCl is 0.079 g (HCl)/g (ChCl-Gly), the absorption equilibrium time is 8min, and the HCl gas with the purity of 99.5 percent can be obtained by heating and desorbing at 90-100 ℃, and after 20 times of cycle tests, the absorption capacity can still reach the level of about 0.079 g (HCl)/g (ChCl-Gly).
Comparative example 1: methanol solvent
Accurately weighing the mass of an absorption bottle with the volume of 10mL, filling a methanol sample, weighing the total mass (the mass of the sample is about 2g, and is accurate to 0.0001 g), introducing HCl pure gas into the absorption bottle filled with the sample for absorption, weighing the mass of the absorption bottle every 2min, recording, and stopping weighing until the difference between the front and the back of weighing is 0.005 g; repeating the absorption experiment step for 3 times to eliminate experiment errors, wherein the error value is +/-2%; calculating the absorption amount of HCl to be 0.683 g (HCl)/g (methanol) at 25 deg.C and HCl partial pressure of 1bar, and the absorption equilibrium time to be 16 min; however, since methanol has a low boiling point (65.7 ℃), when the methanol solvent that has absorbed HCl gas is desorbed by heating, methanol vapor is generated, and 99.5% pure HCl gas cannot be obtained.
Comparative example 2: n-butanol solvent
Comparative example 2 is substantially the same as comparative example 1 except that the sample was changed to n-butanol. At 25 deg.C and HCl partial pressure of 1bar, the absorption amount of HCl is 0.398 g (HCl)/g (butanol), and the absorption balance time is 20 min; however, since butanol has a boiling point of 117 ℃, butanol vapor is generated when the butanol solvent absorbing HCl gas is desorbed by heating, and thus 99.5% pure HCl gas cannot be obtained.
Comparative example 3: glycerol solvent
Comparative example 2 is substantially the same as comparative example 1 except that the sample was changed to glycerin. At a temperature of 25 ℃ and an HCl partial pressure of 1bar, the absorption amount of HCl is 0.271 g (HCl)/g (glycerol), and due to the large viscosity of the glycerol, the HCl absorption rate is slow, the mass transfer resistance is large, and the absorption equilibrium time is as long as 140 min.
FIG. 5 is a diagram of an HCl absorption apparatus, in FIG. 5, V1: gas mixing bottle, V2: gas absorption bottle, F1~F2: a rotameter; j. the design is a square1~J4: and a stop valve. The absorption process is as follows: an absorption bottle (V) filled with choline chloride-glycerin eutectic solvent2) Placing in a water bath thermostat, and connecting a pipeline. Opening valve (J)1) Controlling the flow meter F1The index is 50 mL/min; or open at the same timeValve (J)1、J2) Controlling the flow meter F1Reading is 15 mL/min, flowmeter F2The reading is 85 mL/min. And weighing the mass of the absorption bottle every 2min until the difference between the mass of the absorption bottle and the mass of the absorption bottle before and after weighing is 0.005g, and stopping weighing. The above absorption experiment step was repeated 3 times to calculate the mean value to exclude experimental errors, with an error value of ± 2%.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (10)
1. Application of choline chloride-glycerol eutectic solvent in absorbing HCl gas.
2. A method for absorbing HCl gas using a choline chloride-glycerol eutectic solvent, comprising the steps of: and (2) introducing gas containing HCl into an absorption bottle filled with the choline chloride-glycerol eutectic solvent, absorbing the HCl gas into a liquid phase in a bubbling mode, and discharging the residual gas phase from an exhaust port of the absorption bottle to obtain the choline chloride-glycerol eutectic solvent and the residual gas phase for absorbing the HCl gas respectively.
3. The method of claim 2, wherein: the mol ratio of choline chloride to glycerol in the choline chloride-glycerol eutectic solvent is 1: 1.5-1: 2.5.
4. The method of claim 3, wherein: the mol ratio of choline chloride to glycerol in the choline chloride-glycerol eutectic solvent is 1: 1.5.
5. The method of claim 2, wherein: the temperature of the choline chloride-glycerin eutectic solvent for absorbing HCl is 25-60 ℃, and the absorption time is 20-8 min.
6. The method of claim 5, wherein: the temperature of the choline chloride-glycerol eutectic solvent for absorbing HCl is 25 ℃, and the absorption time is 20 min.
7. The method of claim 2, wherein: the absorption partial pressure of the HCl gas is 0.15 bar-1 bar.
8. The method of claim 7, wherein: the partial pressure of absorption of the HCl gas is 0.15 bar.
9. The method according to any one of claims 2 to 8, wherein: the method also comprises a step of heating the choline chloride-glycerol eutectic solvent for absorbing the HCl gas, so that the choline chloride-glycerol eutectic solvent for absorbing the HCl gas is desorbed to release the HCl gas, and the cyclic application of the choline chloride-glycerol eutectic solvent is realized.
10. The method of claim 9, wherein: the heating temperature is 90-100 ℃, and the heating time is 30 min.
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